This invention relates to a colour photographic silver halide material having a novel cyan coupler.
It is known from JP-N 59 111 645, U.S. Pat. No. 5,008,180 and U.S. Pat. No. 5,686,235 to use 2,5-diacylaminophenols having a sulfonyl group as cyan couplers. However, the colour reproduction and dye stability of the dyes produced from the couplers by chromogenic processing do not meet requirements.
The object of the invention was to provide cyan couplers which are improved with regard to these properties. This object is achieved with the couplers described below.
The present invention accordingly provides a colour photographic silver halide material having a support and at least one photosensitive silver halide emulsion layer which is associated with a cyan coupler of the formula (I): 
in which
R1, R2mean H, alkyl, alkenyl, aryl or hetaryl,
R3 means alkyl, alkenyl, aryl or hetaryl,
Z1 means H or a group eliminable under the conditions of chromogenic development,
Y1 means xe2x80x94COR4, xe2x80x94CO2R4, xe2x80x94CONR4R5, xe2x80x94SO2R4, xe2x80x94SO2NR4R5, xe2x80x94COxe2x80x94CO2R4, xe2x80x94COCONR4R5 or a group of the formula: 
R4 means alkyl, alkenyl, aryl or hetaryl,
R5 means H or R4,
R6 means xe2x80x94Nxe2x95x90or xe2x80x94C(R9)xe2x95x90
R7, R8, R9 mean xe2x80x94OR5, xe2x80x94SR5, xe2x80x94NR4R5, xe2x80x94R5 or Cl and
n means 1 or 2.
Within the formula, the following groups of couplers are preferred:
(1) couplers in which n means 1 and R1 to R9, Z1 and Y1 have the stated meaning.
(2) couplers in which n means 2, Y1 means xe2x80x94COxe2x80x94Y11 and Y11 means alkenyl or hetaryl and R1 to R3 and Z1 have the stated meaning.
(3) couplers in which n means 2, Y1 means xe2x80x94SO2R10, xe2x80x94SO2N(R10)2, xe2x80x94CO2R10, xe2x80x94COCO2xe2x80x94R10 or xe2x80x94COCOxe2x80x94N(R10)2 and R10 means alkyl, aryl, alkenyl or hetaryl and
R1 to R3 and Z1 have the stated meaning.
(4) couplers in which n means 2, Y1 means a residue of the formula: 
xe2x80x83and R1 to R3, R6 to R8 and Z1 have the stated meaning.
(5) couplers in which n means 2, Y1 means a residue of the formula: 
xe2x80x83wherein
R10 means H, Cl, CN, Br, F, alkylcarbonyl, arylcarbonyl, alkylaminocarbonyl, arylaminocarbonyl, alkoxycarbonyl or aryloxycarbonyl and R1 to R3 and Z1 have the stated meaning.
In the formula (I) and the compounds (1) to (4), the substituents have the following preferred meaning:
R1, R2H, alkyl, aryl,
R3 alkyl, aryl,
Z1 H, Cl, alkoxy, aryloxy, alkylthio, arylthio,
R6 xe2x80x94Nxe2x95x90,
R7, R8 xe2x80x94OR5, xe2x80x94NR4R5, xe2x80x94Cl.
Very particularly preferably,
R2 means H and
R4 means alkyl or aryl.
Alkyl and alkenyl residues may be linear, branched or cyclic and in turn be substituted.
Aryl and hetaryl residues may in turn be substituted, wherein aryl is in particular phenyl.
Possible substituents for the alkyl, alkenyl, aryl or hetaryl residues are: alkyl, alkenyl, aryl, hetaryl, alkoxy, aryloxy, alkenyloxy, hydroxy, alkylthio, arylthio, halogen, cyano, acyl, acyloxy, acylamino, wherein an acyl residue may be derived from an aliphatic, olefinic or aromatic carbonic, carboxylic, carbamic, sulfonic, sulfonamido, sulfinic, phosphoric, phosphonic or phosphorous acid.
Examples of compounds according to the invention in which n=2 are:
The compounds according to the invention are produced in an analogous manner to the method stated in U.S. Pat. No. 5,686,235.
The compounds of the formula (I) are preferably used in a quantity of 5 to 2000 mg/m2, in particular of 10 to 1000 mg/m2 and very particularly preferably in a quantity of 20 to 500 mg/m2 of the material.
Examples of colour photographic materials are colour negative films, colour reversal films, colour positive films, colour photographic paper, colour reversal photographic paper, colour-sensitive materials for the dye diffusion transfer process or the silver dye bleaching process. A review may be found in Research Disclosure 37038 (1995) and Research Disclosure 38957 (1996).
The photographic materials consist of a support, onto which at least one photosensitive silver halide emulsion layer is applied. Suitable supports are in particular thin films and sheets. A review of support materials and auxiliary layers applied to the front and reverse sides thereof is given in Research Disclosure 37254, part 1 (1995), page 285 and in Research Disclosure 38957, part XV (1996), page 627.
The colour photographic materials conventionally contain at least one red-sensitive, one green-sensitive and one blue-sensitive silver halide emulsion layer, optionally together with interlayers and protective layers.
Depending upon the type of photographic material, these layers may be differently arranged. This is demonstrated for the most important products:
Colour photographic films such as colour negative films and colour reversal films have on the support, in the stated sequence, 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, magenta-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers. The layers of identical spectral sensitivity differ with regard to their photographic sensitivity, wherein the less sensitive sublayers are generally arranged closer to the support than the more highly sensitive sublayers.
A yellow filter layer is conventionally located between the green-sensitive and blue-sensitive layers which prevents blue light from penetrating into the underlying layers.
Possible options for different layer arrangements and the effects thereof on photographic properties are described in J. Inf. Rec. Mats., 1994, volume 22, pages 183-193 and in Research Disclosure 38957, part XI (1996), page 624.
Colour photographic paper, which is usually substantially less photosensitive than a colour photographic film, conventionally has on the support, in the stated sequence, one blue-sensitive, yellow-coupling silver halide emulsion layer, one green-sensitive, magenta-coupling silver halide emulsion layer and one red-sensitive, cyan-coupling silver halide emulsion layer; the yellow filter layer may be omitted.
The number and arrangement of the photosensitive layers may be varied in order to achieve specific results. For example, all high sensitivity layers may be grouped together in one package of layers and all low sensitivity layers may be grouped together in another package of layers in order to increase sensitivity (DE 25 30 645).
The substantial constituents of the photographic emulsion layers are binder, silver halide grains and colour couplers.
Details of suitable binders may be found in Research Disclosure 37254, part 2 (1995), page 286 and in Research Disclosure 38957, part II.A (1996), page 598.
Details of suitable silver halide emulsions, the production, ripening, stabilisation and spectral sensitisation thereof, including suitable spectral sensitisers, may be found in Research Disclosure 37254, part 3 (1995), page 286, in Research Disclosure 37038, part XV (1995), page 89 and in Research Disclosure 38957, part V.A (1996), page 603.
Photographic materials with camera sensitivity conventionally contain silver bromide-iodide emulsions, which may optionally contain small proportions of silver chloride. Photographic print materials contain either silver chloride-bromide emulsions containing up to 80 wt. % of AgBr or silver chloride-bromide emulsions containing above 95 mol % of AgCl.
Details of colour couplers may be found in Research Disclosure 37254, part 4 (1995), page 288, in Research Disclosure 37038, part II (1995), page 80 and in Research Disclosure 38957, part X.B (1996), page 616. The maximum absorption of the dyes formed from the couplers and the developer oxidation product is preferably within the following ranges: yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan coupler 630 to 700 nm.
In order to improve sensitivity, grain, sharpness and colour separation in colour photographic films, compounds are frequently used which, on reaction with the developer oxidation product, release photographically active compounds, for example DIR couplers which eliminate a development inhibitor.
Details relating to such compounds, in particular couplers, may be found in Research Disclosure 37254, part 5 (1995), page 290, in Research Disclosure 37038, part XIV (1995), page 86 and in Research Disclosure 38957, part X.C (1996), page 618.
Colour couplers, which are usually hydrophobic, as well as other hydrophobic constituents of the layers, are conventionally dissolved or dispersed in high-boiling organic solvents. These solutions or dispersions are then emulsified into an aqueous binder solution (conventionally a gelatine solution) and, once the layers have dried, are present as fine droplets (0.05 to 0.8 xcexcm in diameter) in the layers.
Suitable high-boiling organic solvents, methods for the introduction thereof into the layers of a photographic material and further methods for introducing chemical compounds into photographic layers may be found in Research Disclosure 37254, part 6 (1995), page 292.
The non-photosensitive interlayers generally arranged between layers of different spectral sensitivity may contain agents which prevent an undesirable diffusion of developer oxidation products from one photosensitive layer into another photosensitive layer with a different spectral sensitisation.
Suitable compounds (white couplers, scavengers or DOP scavengers) may be found in Research Disclosure 37254, part 7 (1995), page 292, in Research Disclosure 37038, part III (1995), page 84 and in Research Disclosure 38957, part X.D (1996), pages 621 et seq.
The photographic material may also contain UV light absorbing compounds, optical brighteners, spacers, filter dyes, formalin scavengers, light stabilisers, antioxidants, Dmin dyes, plasticisers (latices), biocides and additives to improve coupler and dye stability, to reduce colour fogging and to reduce yellowing, and others. Suitable compounds may be found in Research Disclosure 37254, part 8 (1995), page 292, in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XII (1995), pages 84 et seq. and in Research Disclosure 38957, parts VI, VIII, IX and X (1996), pages 607 and 610 et seq.
The layers of colour photographic materials are conventionally hardened, i.e. the binder used, preferably gelatine, is crosslinked by appropriate chemical methods.
Suitable hardener substances may be found in Research Disclosure 37254, part 9 (1995), page 294, in Research Disclosure 37038, part XII (1995), page 86 and in Research Disclosure 38957, part II.B (1996), page 599.
Once exposed with an image, colour photographic materials are processed using different processes depending upon their nature. Details relating to processing methods and the necessary chemicals are disclosed in Research Disclosure 37254, part 10 (1995), page 294, in Research Disclosure 37038, parts XVI to XXII (1995), pages 95 et seq. and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), pages 630 et seq. together with example materials.
The magenta couplers preferably comprise those having pyrazolotriazole structures of the formulae (II) or (III): 
in which
X21 means H or a group eliminable under the conditions of chromogenic development,
R21 means optionally substituted alkyl,
R22 means R21 or aryl,
wherein the sum of all the C atoms of the residues R21 and R22 in one coupler molecule is at least 12.
Examples of suitable couplers are: 
Apart from the cyan couplers of the formula (I) according to the invention, further cyan couplers may be used in the same or in another layer.
Examples of these are: 
The DOP scavenger preferably comprises benzofuranones of the formula (IV): 
in which
R41 means alkyl, cycloalkyl, aryl, halogen, SR45, NR46R47, nitro, cyano, SO2R48, COOR49, COR50, hetaryl or hydrogen,
R42 has the same meaning as R41 or means OR52,
R43 and R44 mutually independently mean OR51 or have the meaning of R41,
R45, R49 mutually independently mean alkyl, cycloalkyl, alkenyl, aryl or hetaryl,
R46, R47 mutually independently mean H, R44, COR50, COOR49, SO2R48,
R48, R50 mutually independently mean alkyl, cycloalkyl, alkenyl, aryl, hetaryl or NR40R47,
R51 means hydrogen, alkyl or aryl,
R52 means hydrogen, alkyl, aryl, alkylcarbonyl, alkenylcarbonyl, arylcarbonyl, alkoxycarbonyl, alkenyloxyearbonyl, carbamoyl, alkysulfonyl or arylsulfonyl,
o means 0, 1, 2, 3 or 4 and
p means 0, 1, 2, or 3,
wherein two residues R43 or R44 may in each case mean a fused carbo- or heterocyclic ring or the compound of the formula (IV) is attached to a polymer chain via a residue R43 or R44.
Examples of suitable compounds are: 